Negative resist composition, method for producing relief pattern using the same, and electronic component using the same

Abstract

An object of the present invention is to provide a negative resin composition which can produce a pattern with high sensitivity, high resolution and low line edge roughness in pattern formation by exposure to electron beams or EUV, a method for producing a relief pattern and an electronic component using the negative resist composition. Disclosed is a negative resist composition comprising a phenolic compound (A) which has: two or more phenolic hydroxyl groups per molecule; one or more substituents of one or more kinds selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group per molecule in the ortho-position of any of the phenolic hydroxyl groups; and a molecular weight of 400 to 2,500, wherein the content of the phenolic compound (A) is 70% by weight or more of the total solid content of the negative resist composition.

The invention claimed is: 
     
       1. A negative resist composition comprising a phenolic compound (A) which has: two or more phenolic hydroxyl groups per molecule; one or more hydroxymethyl groups per molecule in the ortho-position of any of the phenolic hydroxyl groups; and a molecular weight of 400 to 2,500,
 wherein the content of the phenolic compound (A) is 70% by weight or more of the total solid content of the negative resist composition; 
 wherein the ratio “Mw/Mn” of the weight average molecular weight “Mw” of the phenolic compound and the number average molecular weight “Mn” of the same is from 1.0 to 1.1; and 
 wherein the phenolic compound (A) is one or more kinds selected from the group consisting of compounds represented by the following chemical formula (1): 
 
       
         
           
           
               
               
           
         
         wherein, each R 1  is independently one selected from the group consisting of a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group and a group represented by the following chemical formula (2), and the aryl group contained in R 1  can contain a hydroxyl group and one or more substituents selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group; each R 2  is independently a hydrogen atom or a monovalent organic group; at least two R 2 s per molecule are hydrogen atoms; R 3  is one selected from the group consisting of a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an acyl group, a cyano group, a nitro group, a hydroxymethyl group and an alkoxymethyl group; n1 is an integer of 1 to 3; n2 is an integer of 0 to 2; n1 and n2 are selected from these ranges so as to satisfy the formula n1+n2≦4; x1 is an integer of 3 to 12; in R 1  and/or R 3 , the phenolic compound (A) has one or more hydroxymethyl groups per molecule in the ortho-position of any of the phenolic hydroxyl groups; and groups represented by the same symbol in the chemical formula (1) can be identical or different; 
       
       
         
           
           
               
               
           
         
         
           wherein, R 4  and R 5  are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; Q is an aryl group or a cycloalkyl group; m is 1 or 2; 
         
         wherein the phenolic compound (A) is one or more kinds selected from the group consisting of compounds represented by the following chemical formulae (a-41) to (a-47): 
       
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           wherein each L is independently a hydrogen atom or the substituent selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group, and at least one L per molecule is a hydroxymethyl group at the ortho-position of the phenolic hydroxyl group. 
         
       
     
     
       2. The negative resist composition according to  claim 1 , further comprising an acid generator (8) which directly or indirectly produces acid by exposure to active energy rays having a wavelength of 248 nm or less, wherein the negative resist composition is a chemically amplified negative resist composition. 
     
     
       3. The negative resist composition according to  claim 2 , further comprising an organic basic compound (C). 
     
     
       4. The negative resist composition according to  claim 1 , wherein the phenolic compound (A) has two or more substituents of one or more kinds selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group per molecule in the ortho-position of any of the phenolic hydroxyl groups, and wherein the negative resist composition substantially comprises no acid generator and is a non-chemically amplified negative resist composition. 
     
     
       5. The negative resist composition according to  claim 1 , wherein the phenolic compound (A) has a glass transition temperature (Tg) of 60° C. or more. 
     
     
       6. The negative resist composition according to  claim 1 , wherein the phenolic compound (A) has three or more substituents of one or more kinds selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group per molecule in the ortho-position of any of the phenolic hydroxyl groups. 
     
     
       7. A method for producing a relief pattern comprising the steps of:
 (i) forming a resist film by applying the negative resist composition defined by  claim 1  to a substrate and heating the same, and 
 (ii) exposing the resist film to electron beams, ion beams, EUV or x-rays and then developing the same. 
 
     
     
       8. The method for producing a relief pattern according to  claim 7 , further comprising the step of heating the resist film after the exposure and before the development. 
     
     
       9. An electronic component at least part of which comprises the negative resist composition defined by  claim 1  or a cured product thereof. 
     
     
       10. A negative resist composition,
 comprising a phenolic compound (A) which has: two or more phenolic hydroxyl groups per molecule; one or more substituents of one or more kinds selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group per molecule in the ortho-position of any of the phenolic hydroxyl groups; and a molecular weight of 400 to 2,500, and an acid generator (B) which directly or indirectly produces acid by exposure to active energy rays having a wavelength of 248 nm or less; 
 comprising no crosslinking agent which is different from the phenolic compound (A); and 
 being a chemically amplified negative resist composition, 
 wherein the content of the phenolic compound (A) is 70% by weight or more of the total solid content of the negative resist composition; 
 wherein the ratio “Mw/Mn” of the weight average molecular weight “Mw” of the phenolic compound and the number average molecular weight “Mn” of the same is from 1.0 to 1.1; and 
 wherein the phenolic compound (A) is one or more kinds selected from the group consisting of compounds represented by the following chemical formulae (a-1), (a-2), a-7) to (a-8), (a-11), (a-13) to (a-21), (a-23) to (a-25), (a-27) to (a-32), (a-34) to (a-35), (20), (27), (29) and (31): 
 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         wherein each L is independently a hydrogen atom or the substituent selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group, and at least one L per molecule is the substituent selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group at the ortho-position of the phenolic hydroxyl group. 
       
     
     
       11. A method for producing a relief pattern comprising the steps of:
 (i) forming a resist film by applying the negative resist composition defined by  claim 10  a substrate and heating the same, and 
 (ii) exposing the resist film to electron beams, ion beams, EUV or x-rays and then developing the same. 
 
     
     
       12. An electronic component at least part of which comprises the negative resist composition defined by  claim 10  or a cured product thereof. 
     
     
       13. A negative resist composition,
 comprising a phenolic compound (A) which has: two or more phenolic hydroxyl groups per molecule; one or more substituents of one or more kinds selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group per molecule in the ortho-position of any of the phenolic hydroxyl groups; and a molecular weight of 400 to 2,500; a solvent which is one or more kinds selected from the group consisting of diethylene glycol dimethyl ether, cyclohexanone, cyclopentanone, 1-ethoxy-2-propanol, ethyl lactate, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; and a photoacid generator which is in a content of less than 1 part by weight with respect to 100 parts by weight of the phenolic compound (A); 
 comprising no crosslinking agent which is different from the phenolic compound (A); and 
 being a non-chemically amplified negative resist composition, 
 wherein the content of the phenolic compound (A) is 70% by weight or more of the total solid content of the negative resist composition; 
 wherein the ratio “Mw/Mn” of the weight average molecular weight “Mw” of the phenolic compound and the number average molecular weight “Mn” of the same is from 1.0 to 1.1; and 
 wherein the phenolic compound (A) is one or more kinds selected from the group consisting of compounds represented by the following chemical formulae (a-1), (a-2), (a-7) to (a-8), (a-11), (a-13) to (a-21), (a-23) to (a-25), (a-27) to (a-32), (a-34) to (a-35), (20), (27), (29) and (31): 
 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       wherein each L is independently a hydrogen atom or the substituent selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group, and at least one L per molecule is the substituent selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group at the ortho-position of the phenolic hydroxyl group. 
     
     
       14. A method for producing a relief pattern comprising the steps of:
 (i) forming a resist film by applying the negative resist composition defined by  claim 13  a substrate and heating the same, and 
 (ii) exposing the resist film to electron beams, ion beams, EUV or x-rays and then developing the same. 
 
     
     
       15. An electronic component at least part of which comprises the negative resist composition defined by  claim 13  or a cured product thereof.